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  • B82—NANOTECHNOLOGY
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  • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
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  • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
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  • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
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  • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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  • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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  • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
  • C09D7/40—Additives
  • C09D7/60—Additives non-macromolecular
  • C09D7/61—Additives non-macromolecular inorganic
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  • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
  • C09D7/40—Additives
  • C09D7/60—Additives non-macromolecular
  • C09D7/61—Additives non-macromolecular inorganic
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  • C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
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  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/34—Silicon-containing compounds
  • C08K3/36—Silica

Definitions

• Dispersion comprising hydrophobized silicon dioxide particles
• the invention relates to an aqueous dispersion which comprises hydrophobized silicon dioxide particles, and to the preparation and use thereof.
• the invention further relates to a formulation which comprises hydrophobized silicon dioxide particles, and to the preparation and use thereof .
• dispersions Important factors in the preparation of dispersions are: • good wetting of the fillers and pigments during processing. This allows the dispersion times and the introduction of dispersion energy to be reduced; often, a very low viscosity of the dispersions is desired; • after drying, a high shine should be achieved; the settling tendency of the solid phase of the dispersion should be at a minimum, including in the course of prolonged storage, transport over large distances and under extreme climatic stress; • no flocculation should occur in the dispersion; this is of particular significance in the production of reproducible hues in the case of use of nowadays customary colour mixing machines; the dispersion should be compatible with a multitude of additives.
• dispersants are generally added to the dispersion.
• dispersants based on inexpensive ionic structures such as polyphosphates (Ullmann's
• DE-A-10316661 discloses a highly filled, low-viscosity dispersion which contains 5 to 50% by weight of hydrophobized silicon dioxide particles, and a dispersant of the general formula R ⁇ COO- (CH 2 -CH (Ph) -O) a - (C n H 2n - ⁇ R 2 ⁇ -O) b -R 3 •
• this dispersion leads only to moderately long-lasting coatings in the application.
• the invention provides an aqueous dispersion which comprises hydrophobized silicon dioxide particles and in each case one or more dispersing additives, a basic composition, and which is free of colour pigments, inactive fillers and binders, characterized in that the hydrophobized silicon dioxide particles have a methanol wettability of 30 to 60, preferably 35 to 55, and are present in the dispersion with a proportion of 0.1 to 50% by weight, preferably 10 to 30% by weight, - the proportion of water is 30 to 90% by weight, preferably 50 to 70% by weight, based in each case on the dispersion, the dispersing additive is at least one phosphate ester of an ethoxylated alcohol having 8 to 18 carbon atoms, the proportion of which is 3 to 25% by weight, preferably 6 to 20% by weight and more preferably 9 to 16% by weight, based in each case on the proportion of the hydrophobized silicon dioxide particles, the basic composition comprises or consists of one or more amines of the general formula RNH2, R2NH and R3
• hydrophobicity of the hydrophobized silicon dioxide particles used in the inventive dispersion has to be observed.
• hydrophobicity of the silicon dioxide particles is too high or too low, this has adverse effects on the stability of the inventive dispersion.
• a suitable measure of the hydrophobicity is the methanol wettability.
• methanol wettability in each case 0.2 g ( ⁇ 0.005 g) of hydrophobic silicon dioxide particles is weighed into transparent centrifuge tubes. 8.0 ml of a methanol/water mixture containing one of 10, 20, 30, 40, 50, 60, 70 and 80% by volume of methanol are added to each weighed sample. The closed tubes are shaken for 30 seconds and then centrifuged at 2500 min "1 for 5 minutes. The sediment volumes are read off, converted to per cent and plotted graphically against the methanol content (% by volume) . The turning point of the curve corresponds to the methanol wettability. The higher the methanol wettability, the greater the hydrophobicity of the silicon dioxide particles.
• the methanol wettability is 30 to 60.
• Suitable commercially obtainable hydrophobized silicon dioxide particles which meet this condition are, for example, AEROSIL ® R972, AEROSIL ® R974, AEROSIL ® R104 , AEROSIL ® R106 and AEROSIL ® R9200 , all from Evonik Degussa.
• the hydrophobized silicon dioxide particles can preferably be obtained by hydrophobizing fumed silicon dioxide particles.
• Fumed particles are understood to mean those produced by flame hydrolysis or flame oxidation. Fumed silicon dioxide particles are described, for example, in Ullmann' s Encyclopedia of Industrial Chemistry, Vol. A23, page 635, 5 th Edition. These particles are generally present in the form of aggregated primary particles and have, on their surface, reactive sites which can react with a hydrophobizing agent.
• the hydrophobized silicon dioxide particles used for the inventive dispersion preferably have a BET surface area of 50 to 300 m 2 /g, more preferably of 70 to 200 m 2 /g and most preferably of 90 to 150 m 2 /g.
• hydrophobized silicon dioxide particles in the inventive dispersion have a mean particle size (median) of 200 nm or less. Particular preference is given to a range of 100 to 200 nm.
• a further essential constituent of the inventive dispersion is at least one phosphate ester of an ethoxylated alcohol which contains 8 to 18 carbon atoms.
• the dispersion preferably comprises a mono-, di- and/or trisubstituted phosphate ester of an ethoxylated primary alcohol with one, two or three linear Ci 2 -Ci 4 carbon chains.
• the inventive dispersion comprises a basic composition which comprises or consists of one or more amines of the general formula RNH2, R2NH and R3N.
• the basic composition preferably consists of one or more amines of the general formula RNH 2 , R 2 NH and R3N.
• This amine is preferably a primary, secondary or tertiary amine or an amino alcohol having in each case 2 to 10 carbon atoms.
• Suitable compounds are, for example, monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, triisopropanolamine, N, N- dimethylisopropanolamine, 3-amino-l-propanol, l-amino-2- propanol, 2-amino-2-methyl-l-propanol, 2-pyrrolidone, N-methyl-2-pyrrolidone, N-ethylpyrrolidone, N-vinyl- pyrrolidone, 1, 3-dimethylimidazolidone and piperidine.
• an inventive dispersion which comprises N, N-dimethylethanolamine (Me2N (CH 2 ) 2OH) .
• a further essential constituent of the inventive dispersion is a polyol which contains 2 to 15 carbon atoms.
• the polyol is preferably selected from the group comprising ethylene glycol, propylene glycol, butylene glycol, diethylene glycol, triethylene glycol, tripropylene glycol, trimethylolpropane, pentaerythritol, neopentyl glycol, glycerol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, dipropylene glycol monoethyl ether, acetylene glycols such as 2, 4, 7, 9-to J -i3:u ⁇ t,r- ⁇ l ⁇ oc-?- ⁇ :.c-4, 7 - J--C 1, cr ⁇ ooLvlone q ⁇ ⁇ w/ Jeriv'1'.ives,
• the inventive dispersion may preferably comprise tripropylene glycol, 2, 4, 7, 9-tetramethyldec-5-yne-4, 7-diol or a mixture of the two.
• the inventive aqueous dispersion may further comprise N-methyl-2-pyrrolidone.
• the proportion of N-methyl-2- pyrrolidone is preferably 1 to 20% by weight based on the proportion of hydrophobized silicon dioxide particles.
• an aqueous dispersion which comprises N, N- dimethylethanolamine and l-methyl-2-pyrrolidone may be advantageous .
• the inventive dispersion may further comprise one or more preferably silicone-free defoamers.
• the proportion thereof is preferably 0.5 to 5% by weight and more preferably 1 to 3% by weight, based in each case on the proportion of hydrophobized silicon dioxide particles.
• a particularly advantageous inventive dispersion has been found to be one which - has a pH of 9 to 11 and contains 10 to 30% by weight, based on the dispersion, of hydrophobic silicon dioxide particles with a methanol wettability of 40 to 50, with a BET surface area of 90 to 150 m 2 /g, - 9 to 16% by weight, based on the proportion of hydrophobized silicon dioxide particles, of a mono-, di- and/or trisubstituted phosphate ester of an ethoxylated primary alcohol having one, two or three linear C12-C14 carbon chains, - 5 to 20% by weight, based on the proportion of hydrophobized silicon dioxide particles, of N, N- dimethyIethanolamine,
• a suitable dispersion apparatus for preparing the inventive aqueous dispersion is any apparatus which is capable of enabling intensive wetting of the hydrophobic powder with the aqueous phase.
• dissolvers In the coatings industry, it is common practice to use dissolvers for this purpose, the relatively simple construction of which enables a mode of production which is low in maintenance and easy to clean. According to the required viscosity or else filling level of the aqueous dispersion of hydrophobic fumed silica to be obtained, however, intensive dispersion or post-grinding is necessary.
• the post-grinding can be effected, for example, in stirred ball mills.
• intensive shearing with the aid of rotor/stator machines is sufficient in many cases.
• An appropriate combination of wetting and dispersing means is that of the rotor/stator machines from Ystral, which enable the powder to be sucked in and, after the closure of the powder intake orifice, to be dispersed with intensive shearing.
• the invention further provides a formulation which comprises hydrophobized silicon dioxide particles, one or more binders, one or more dispersing additives and a basic composition, in which the hydrophobized silicon dioxide particles have a methanol wettability of 30 to 60, preferably 35 to 55, and are present in the formulation with a proportion of 0.05 to 5% by weight, - the dispersing additive is at least one phosphate ester of an ethoxylated alcohol having 8 to 18 carbon atoms, the proportion of which is 3 to 25% by weight, preferably 6 to 20% by weight and more preferably 9 to 16% by weight, based in each case on the proportion of the hydrophobized silicon dioxide particles, the basic composition comprises or consists of one or more amines of the general formula RNH2, R2NH and R3N, where R is an alkyl group or a hydroxyl-substituted alkyl group having 2 to 10 carbon atoms, which may be substituted or unsubstituted, linear or branched, acyclic or
• Suitable binders may be the resins customary in paints and coatings technology, as described, for example, in "Lackharze, Chemie, compassion und füren [Coating resins, chemistry, properties and applications], Eds. D. Stoye, W. Freitag, Hanser Verlag, Kunststoff, Vienna, 1996".
• Examples include the polymers and copolymers of (meth) acrylic acid and esters thereof, optionally bearing further functional groups, with further olefinically unsaturated compounds, for example styrene, polyetherpolyols, polyesterpolyols, polycarbonatepolyols, polyurethanepolyols and epoxy resins, and also any mixtures of these polymers, and also fatty acid-modified "alkyd resins" prepared by polycondensation, as described in Ullmann, 3 rd Edition, Volume 11, page 334 ff.
• further olefinically unsaturated compounds for example styrene, polyetherpolyols, polyesterpolyols, polycarbonatepolyols, polyurethanepolyols and epoxy resins, and also any mixtures of these polymers, and also fatty acid-modified "alkyd resins" prepared by polycondensation, as described in Ullmann, 3 rd Edition, Volume 11, page 3
• polymer components used may be organic compounds bearing hydroxyl groups, for example polyacrylate-, polyester-, polycaprolactone-, polyether-, polycarbonate- and polyurethanepolyols, and hydroxy- functional epoxy resins, and also any mixtures of these polymers.
• organic compounds bearing hydroxyl groups for example polyacrylate-, polyester-, polycaprolactone-, polyether-, polycarbonate- and polyurethanepolyols, and hydroxy- functional epoxy resins, and also any mixtures of these polymers.
• aqueous or solvent-containing or solvent-free polyacrylate- and polyesterpolyols and any mixtures thereof are used.
• Polyacrylatepolyols are copolymers of monomers, some of which have hydroxyl groups, with other olefinically unsaturated monomers, for example esters of (meth) acrylic acid, styrene, alpha-methylstyrene, vinyltoluene, vinyl esters, mono- and dialkyl maleates and fumarates, alpha- olefins and further unsaturated oligomers and polymers.
• the inventive formulation may further comprise colour pigments and/or inactive fillers.
• the colour pigments may be of organic or inorganic nature. Examples include barium sulphate, lead oxides, lead silicates, iron oxides, phthalocyanine complexes, titanium dioxides, zinc oxides and zinc sulphide.
• the inventive formulation may further comprise inactive fillers.
• Inactive fillers are understood to mean fillers which are known to those skilled in the art and influence the rheological properties of the formulation only insignificantly, if at all. Examples include calcium carbonate, diatomaceous earth, mica, kaolin, chalk, quartz and talc.
• Colour pigments and/or inactive fillers are typically present in proportions totalling 10 to 70% by weight, preferably 30 to 50% by weight, based on the total solids content of the formulation.
• the total solids content of the formulation which is composed of hydrophobized silicon dioxide particles, binders and any colour pigments and inactive fillers, is preferably 40 to 60% by weight based on the formulation.
• the invention further provides a process for preparing the formulation, in which the inventive aqueous dispersion is used.
• the invention further provides for the use of the inventive aqueous dispersion or of the inventive formulation as an additive to waterborne surfacers in the automobile industry, as a coating constituent in can- and coil-coating processes, as an additive in water-based UV-curable formulations, for example for wood protection, and as a constituent of coating protection films.
• Example 1 (according to invention) : 6.36 kg of Hydropalat 7003 from Cognis, 1.27 kg of dimethylethanolamine (DMEA), 0.19 kg of BYK ® 011 from Byk Chemie, 0.19 kg of Surfynol ® 104 from Air Products, 1.91 kg of l-methyl-2-pyrrolidone and 0.63 kg of tripropylene glycol were introduced with stirring into 21.19 kg of water.
• DMEA dimethylethanolamine
• BYK ® 011 from Byk Chemie
• Surfynol ® 104 from Air Products
• 1.91 kg of l-methyl-2-pyrrolidone and 0.63 kg of tripropylene glycol were introduced with stirring into 21.19 kg of water.
• Example 2 A jacketed dispersing vessel is initially charged with 312.5 g of demineralized water, 100.0 g of Hydropalat ® 7003, 6.0 g of DMEA, 3.0 g of BYK ® 011, 3.0 g of Surfynol ® 104 E, 30.0 g of l-methyl-2- pyrrolidone and 10.0 g of tripropylene glycol, which were mixed with the aid of a Dispermat ® laboratory dissolver from VMA-Getzmann GmbH (toothed disc of diameter 70 mm) at 200 revolutions per minute. Aerosil ® R972 was then added in portions and dispersed at 2400 revolutions per minute. After approx. 80 g of Aerosil ® R972, further Aerosil ® R972 is added in alternation with further water (total of
• Aerosil ® R972 339.5 g of water. At 170 g of Aerosil ® R972, the entire amount of water had been added. Then a further 30 g of Aerosil ® R972 and 6 g of DMEA are incorporated in alternation into the dispersion. In total, 200 g of Aerosil ® R972 were incorporated (20 per cent dispersion) .
• dispersion is continued with the dissolver at 2400 revolutions per minute for a further 15 min.
• dispersion is finally dispersion at 7000 revolutions per minute with the aid of an Ultra Turrax (rotor/stator dispersion unit of the Ultra- Turrax T50 type from Ika-Werke with the S50N-G45G dispersion tool) for 30 min.
• the jacketed dispersing vessel is cooled with water, such that the temperature is approx. 30 0 C.
• the pH of the dispersion is 10.2, the viscosity 82 mPas at 10 s '1 and 72 mPas at 100 s '1 (all viscosity values reported in the examples are based on a temperature of 23°C) .
• Example 3 (according to invention) : A jacketed dispersing vessel is initially charged with 312.5 g of demineralized water, 100.0 g of Hydropalat ® 7003, 6.0 g of DMEA, 3.0 g of BYK ® 011, 3.0 g of Surfynol ® 104 E, 30.0 g of l-methyl-2- pyrrolidone and 10.0 g of tripropylene glycol, which are mixed with the aid of a Dispermat ® laboratory dissolver from VMA-Getzmann GmbH (toothed disc of diameter 70 mm) at 200 revolutions per minute. Aerosil ® R974 was then added in portions and dispersed at 2400 revolutions per minute. After approx.
• Aerosil ® R974 70 g of Aerosil ® R974, further Aerosil ® R974 is added in alternation with further water (total of 339.5 g of water). At 170 g of Aerosil ® R974, the entire amount of water had been added. Then a further 30 g of Aerosil ® R974 and 6 g of DMEA are incorporated in alternation into the dispersion. Subsequently, dispersion is continued with the dissolver at 2400 revolutions per minute for a further 15 min.
• the pH of the dispersion is 10.1, the viscosity 1036 mPas at 10 s "1 and 390 mPas at 100 s "1 .
• Example 4 (comparative) : A jacketed dispersing vessel is initially charged with 312.5 g of demineralized water, 100.0 g of Hydropalat ® 7003, 6.0 g of DMEA, 3.0 g of BYK ® 011, 3.0 g of Surfynol ® 104 E, 30.0 g of l-methyl-2- pyrrolidone and 10.0 g of tripropylene glycol, which are mixed with the aid of a Dispermat ® laboratory dissolver from VMA-Getzmann GmbH (toothed disc of diameter 70 mm) at 200 revolutions per minute. Aerosil ® R202 was then added in portions and dispersed at 2400 revolutions per minute. The powder is wetted very poorly and is dispersed in only poorly. After only 44 g (9% by weight), the dispersion became very viscous and no further Aerosil ® R202 could be incorporated.
• Example 5 A jacketed dispersing vessel is initially charged with 312.5 g of demineralized water, 6.0 g of DMEA, 3.0 g of BYK ® 011, 3.0 g of Surfynol ® 104 E, 30.0 g of l-methyl-2-pyrrolidone and 10.0 g of tripropylene glycol, which are mixed with the aid of a Dispermat ® laboratory dissolver from VMA-Getzmann GmbH (toothed disc of diameter 70 mm) at 200 revolutions per minute. Aerosil ® R972 was then added in portions and dispersed at 2400 revolutions per minute. The powder is wetted very poorly and is dispersed in only poorly. After only 40 g (10% by weight), the dispersion became very viscous.
• Example 6 (comparative) : A jacketed dispersing vessel is initially charged with 312.5 g of demineralized water, 100.0 g of Hydropalat ® 7003, 6.0 g of DMEA, 3.0 g of BYK ® 011, 3.0 g of Surfynol ® 104 E and 30.0 g of l-methyl-2- pyrrolidone, which are mixed with the aid of a Dispermat ® laboratory dissolver from VMA-Getzmann GmbH (toothed disc of diameter 70 mm) at 200 revolutions per minute. Aerosil ® R972 was then added in portions and dispersed at 2400 revolutions per minute. After approx. 80 g of Aerosil ®
• Aerosil ® R972 is added in alternation with further water (total of 339.5 g of water) .
• further water total of 339.5 g of water
• Aerosil ® R972 the entire amount of water had been added.
• a further 40 g of Aerosil ® R972 and 6 g of DMEA are incorporated in alternation into the dispersion.
• 200 g of Aerosil ® R972 were incorporated (20% dispersion) .
• dispersion is continued with the dissolver at 2400 revolutions per minute for a further 15 min.
• dispersion is finally dispersion at 7000 revolutions per minute with the aid of an Ultra Turrax (rotor/stator dispersion unit of the Ultra- Turrax T50 type from Ika-Werke with the S50N-G45G dispersion tool) for 30 min.
• the jacketed dispersing vessel is cooled with water, such that the temperature is approx. 30 0 C.
• the pH of the dispersion is 10.1, the viscosity 69 mPas at 10 s '1 and 57 mPas at 100 s "1 .
• Example 7 100 g of Aerosil ® R972 are incorporated by means of a dissolver at a setting of approx.
• the actual dispersion is subsequently effected with the aid of an Ultra Turrax at 7000 rpm for 30 minutes.
• d 5 o(v> is 193 nm; the viscosity is 310 mPas at 10 s '1 , and 275 mPas at 100 s "1 .
• Table 1 shows the composition and properties of the dispersions of Examples 1 to 7.
• Inventive Examples 1 to 3 lead to dispersions with low viscosity, which increases only insignificantly even in the course of prolonged storage.
• Table 2 reproduces the values of the viscosity (in mPas) of the dispersion prepared in Example 1 as a function of the shear rate (in s '1 ) , immediately after the preparation of the dispersion, after 1 month of storage and after 6 months of storage.
• the mean particle diameter d 5 o (median) of the hydrophobized silicon dioxide particles behaves analogously. It is 156 nm immediately after preparation, 174 nm after 1 month of storage and 194 nm after 6 months of storage.
• Figure 1 shows the viscosity (in mPas) as a function of the pH. In the range from 9 to 11, the dispersion exhibits a particularly low viscosity. At pH values less than 9, the viscosity rises again.
• This structural viscosity leads to an increase in the stability of a dispersion which, for example, also comprises fillers and/or colour pigments, since it greatly reduces the settling thereof.
• Table 2 Viscosity of the dispersion from Example 1 as a function of shear rate and storage
• Comparative Example 4 shows the influence of the methanol wettability of the hydrophobized silicon dioxide particles used.
• Aerosil ® R202 with a methanol wettability of 75 is used, compared to Aerosil ® R972 in Inventive Examples 1 and 2.
• Aerosil ® R972 and Aerosil ® R974 have comparable BET surface areas. Nevertheless, only small proportions can be incorporated.
• Inventive Example 3 shows that Aerosil ® R974 with a higher BET surface area than Aerosil ® R972 but with a comparable methanol wettability can also be incorporated in high proportions.
• Comparative Example 5 shows the influence of the phosphate ester on the properties of the inventive dispersion.
• the hydrophobized silicon dioxide particles are wetted very poorly and the result is high-viscosity dispersions with a low filler content.
• Comparative Example 6 shows the influence of the polyol on the properties of the inventive dispersion. Without a sufficient amount of polyol, sufficient foaming of the dispersion is not ensured. In the particle size determination, fractions with a high diameter are determined.
• Comparative Example 7 is taken from DE-A-10316661 (Example 1 there) .
• Table 1 shows that the viscosity of this dispersion is about four times higher than the viscosity of the inventive dispersion from Examples 1 and 2.
• Bayhydrol D 270 water-dilutable polyester resin from Bayer AG; Tronox ® R-FD-I, titanium dioxide from Kerr McGee Pigments GmbH & Co. KG), Bayferrox ® 303 T, iron oxide black, Bayer AG; Blanc fixe Micro, barium sulphate, Sachtleben GmbH; Micro Talc IT Extra, talc, Norwegian Talc; BYK ® 011, silicone-f ree defoamer, from Byk Chemie; Surfynol ® 104E, 2,4,7, 9-tetramethyldec-5-yne-4,7-diol, from Air Products
• Bayhytherm 3146 aliphatic, self-crosslinking urethane resin, Bayer AG; Cymel ® 327, melamine resin, Dyno Cytec; Byk ® 346, polyether-modified dimethylpolysiloxane solution
• Borchi Gel PW 25 from Borchers; structurally viscous thickener for adjusting the viscosity in the low and moderate shear segment;
• Dispersion Disperse millbase with Dispermat SL 603, 100 ml of 1 mm glass beads, at 3000 rpm, until grindometer ⁇ 10 ⁇ m.
• Viscosity of the coating materials -Coating materials: Flow curves and yield tests
• Runoff behaviour The run limit at which no runs extend down to the next thickest strip was assessed.
• Table 12 Maximum layer thickness in ⁇ m
• Figures 2 and 3 show the flow and yield curves of formulations (coating materials) based on resins C and D.
• ⁇ coating material CO
• • coating material C2
• 0 coating material C4
• ⁇ coating material C6.

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